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Transition into non-monotonic approach to equilibrium in geminate exchange reaction

Summary: Transition into non-monotonic approach to equilibrium
in geminate exchange reaction
Alexander V. Popov 1
, Noam Agmon *
Department of Physical Chemistry and The Fritz Haber Research Center, The Hebrew University, Jerusalem 91904, Israel
Received 1 October 2002; in final form 4 October 2002
Modern laser-chemistry techniques allow the preparation of initially correlated pairs as precursors to electron or
atom exchange in solution. We obtain a rigorous analytic solution for the two coupled ‘backward’ diffusion equations
describing the survival and reaction probabilities. Investigating its long-time asymptotic behavior reveals a transition
from monotonic to non-monotonic approach to equilibrium, usually unexpected for elementary single-step reactions.
We suggest the synthesis of ‘detachable bifunctional compounds’, that may undergo peculiar kinetics as described
” 2003 Elsevier Science B.V. All rights reserved.
1. Introduction
While classical bimolecular chemical kinetics
deals with homogeneously distributed reactants
[1], modern laser techniques of chemical physics
enable the preparation of reacting (geminate) pairs
at close proximity. Examples include ion (or ion≠


Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem


Collections: Chemistry